CN101468838B - Method for preparing composite water purification agent - Google Patents
Method for preparing composite water purification agent Download PDFInfo
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- CN101468838B CN101468838B CN2007101591278A CN200710159127A CN101468838B CN 101468838 B CN101468838 B CN 101468838B CN 2007101591278 A CN2007101591278 A CN 2007101591278A CN 200710159127 A CN200710159127 A CN 200710159127A CN 101468838 B CN101468838 B CN 101468838B
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- oxygenant
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Abstract
The invention discloses a method for manufacturing a compound water purifying agent suitable for treating mine sewage. The process of the method comprises: using fly ash and hydrochloric acid as main materials; carrying out acid dissolution treatment, sedimentation and filtration to obtain a solution of aluminum and ferric salts; adding an oxidizer, an accelerant and an organic polymer additive for oxidation, hydrolytic polymerization, and copolymerization; aging the mixture; and obtaining the liquid water purifying agent or drying the liquid water purifying agent to obtain a solid water purifying agent product. The water purifying agent is characterized by being manufactured by using the fly ash solid waste produced in a coal-fired power plant as a main material and the natural polymer additive. The method for manufacturing the water purifying agent overcomes the drawbacks in the prior manufacturing of water purifying agents and achieves a safe, nontoxic and pollution-free manufacturing process as well as energy-saving and environment-protection effects. The product of the method has the combined mechanisms of various purifying agents, the combined advantages of organic and inorganic purifying agents and strong adaptability to the conditions of sewage. The product is particularly used for treating mine sewage and represents the characteristics of novelty, high efficiency and environment protection.
Description
Technical field
The invention belongs to water-treatment technology field, relate to water treatment with the production method of agent, specifically is that the coal powder that adopts the coal-burning power plant to produce is the making method that raw material production a kind of is used to handle the composite water purifying agent of mine high-turbidity sewage.
Background technology
In recent years, progress along with water technology, the coagulating agent research and development have obtained very fast development, and the development of novel water purification agent emerges in an endless stream, and inorganic water purification agent can reduce molysite and aluminium salt two big classes substantially, the organic polymer coagulating agent is representative with the polyacrylamide, inorganic coagulant and organic coagulating agent respectively have relative merits in actual applications, and the limitation of application is also respectively arranged, even sometimes, all can produce secondary pollution in various degree, be unfavorable for the utilization again after the water treatment.The NEW TYPE OF COMPOSITE water purification agent integrates multiple purification mechanism on purification mechanism, have the advantage of organic and inorganic water purification agent concurrently; On molecular structure, totally be chain-like structure, have active branch, soluble in water, stable performance, temperature influence is little, and is especially strong to sewage condition adaptability, pointed to the mine sewage disposal.But the cost of producing this composite water purifying agent at present is too high, makes most of bargh not accept;
In order to solve the existing high problem of water purification agent cost, at present, it is the main material production composite water purifying agent in exploitation with solid waste-flyash that the coal-burning power plant produces that the lot of domestic and international people is arranged, and utilizes the Al that contains more amount in the flyash
2O
3, Fe
2O
3, effective ingredients such as FeO, gac, active silicic acid make water purification agent, obtain certain achievement.China power plant is mainly based on thermal power generation, several ten million tons of annual discharge coal ash amounts, raw material sources are extensive, cheap, be main raw material with flyash, refuse is utilized effectively, turn waste into wealth, simultaneously also reduce environmental pollution, improved resource utilization, conformed to the fundamental policy of national energy-saving and emission-reduction.For example, the patent No. is that 01128398.X discloses the method for producing inorganic Al-Fe polymerized coagulant with flyash, this method is making on the aluminium chloride ferrum solution basis, institute adds inorganic calcium aluminate powder and only plays the basicity effect of adjusting, owing to lack oxidation, hydrolysis, polyreaction, the water purification agent relative molecular weight that makes is low, aspect flocculation ability, raising settling velocity, to the thermal adaptability aspect, especially to high turbidity mine wastewater processing aspect, effect is bad.Application number is 20061001714.1 to disclose a kind of method of utilizing flyash to produce inorganic Al-Fe polymerized coagulant, its technology is complicated, and on synthesis mechanism, there is not essence different with common synthesis method, comparatively speaking, the water purification agent that this method is made still exists the water purification agent relative molecular weight low, poor at flocculation ability, settling velocity is low, poor to thermal adaptability, especially to the characteristics of high turbidity purificating raw water weak effect, the like product of selling on decontamination effect improving and the market is close, aspect the high-turbidity water processing of mine, DeGrain.
Summary of the invention
Problems such as complex manufacturing technology, the processing mine sewage ability of costing an arm and a leg at existing water purification agent the invention discloses a kind of making method of NEW TYPE OF COMPOSITE water purification agent; with flyash is main raw material; composite water purifying agent at the research and development of the water quality characteristics of mine sewage; embody characteristics novel, efficient, environmental protection; reached the treatment of wastes with processes of wastes against one another, the purpose of resources conseravtion and environment.
The present invention is to be that major ingredient is made on the technology basis of polymeric aluminum molysite flocculation agent at flyash, further add organic pluronic polymer starch or Mierocrystalline cellulose and reaction promotor in oxidation, hydrolytic polymerization, copolymerization stage, synthesized composite water purifying agent, it is the difference with such polymeric ferric aluminum salt as water purifying agent manufacture craft maximum.
The object of the present invention is achieved like this:
Main raw material is flyash, hydrochloric acid, oxygenant, promotor and organic polymer auxiliary agent, and its proportioning is (pressing solid weight per-cent) 30%～35%, 50%～55%, 10%～15%, 1%～1.5%, 1%～1.5%, and its technical process is:
With flyash, hydrochloric acid is raw material, and---------filtration obtains the ferro-aluminum saline solution, and------oxidation, hydrolytic polymerization, copolyreaction---slaking---are isolated liquid water purification agent product or are continued drying and obtain the solid water purifier product to add oxygenant promotor, organic polymer auxiliary agent in sedimentation in sour molten processing.
Making method of the present invention is as follows, and levigate extremely-200 orders of raw material powder coal ash are accounted for more than 90%; Add 50～60 ℃ of concentration in proportion and be 37% hydrochloric acid and carry out sour molten reaction, the sour molten reaction times is 2～3 hours, and cooled and filtered makes the ferro-aluminum saline solution; Again with oxygenant (as H
2O
2) add the ferro-aluminum saline solution, in the time of 55～65 ℃, carry out the oxydrolysis polyreaction, about about 1.5～2 hours; Be warmed up to 80～90 ℃, add promotor (as ammonium persulphate), add the starch or the Mierocrystalline cellulose auxiliary agent (general compound concentration is 10%) that have prepared again, carry out copolyreaction, maintain the temperature at 80～90 ℃, pressure is at 2～2.5 normal atmosphere, and the reaction times was at 4～5 hours; Carry out maturing process then, carry out at normal temperatures, the time is 8～10 hours, through separating, obtains composite fluid water purification agent product or continue drying obtaining composite solid water purification agent product.
The organic polymer auxiliary agent that the present invention uses is: starch or Mierocrystalline cellulose, selecting these two kinds of auxiliary agents mainly is wherein to contain than polyhydroxy functional groups, may with polymeric aluminum molysite generation copolymerization, its raw materials cost is lower in addition, be the natural polymer organic products, nontoxic, can improve product performance, make decontamination effect improving better.
The oxygenant that the present invention uses is: H
2O
2, the vitriol oil, concentrated nitric acid etc., the selective oxidation agent mainly acts on and is: the ferrous iron that exists in the raw material generates ferrous salt after the molten reaction of acid, generate molysite after the oxidation, and the hydrolysis ability of molysite is more eager to excel in whatever one does than ferrous salt.
The promotor that the present invention uses is: ammonium persulphate (or cerium ammonium nitrate etc.).The selection of promotor is relevant with the selection of oxygenant, when oxygenant selects H
2O
2When (or vitriol oil), promotor is selected ammonium persulphate; When oxygenant selects dense HNO
3The time, promotor is selected cerium ammonium nitrate, and the system that forms promotes the effective of copolyreaction like this.
The purpose that the present invention introduces the organic polymer auxiliary agent is further to improve the purifying property of the inorganic water purification agent of polymeric aluminum molysite, make flocculation settling velocity faster, especially with strong points to the mine former water purification of high turbidity, can make purification more thorough, decontamination effect improving is better, and can reduce dosing, reduce the secondary pollution that medicament exists water body, (it is very little that organic additive accounts for material rate to reduce the purification cost, it is very little that medicament is manufactured the cost increase rate), and these two kinds of auxiliary agents are not used at water treatment field at present.
The present invention is a main raw material with solid waste-flyash that the coal-burning power plant produces, and is equipped with the natural organic high-molecular auxiliary agent and makes.Its method overcomes existing weak point of making water purification agent, and making processes is simple to operation, safety non-toxic is pollution-free, plays the effect of save energy, protection environment.The water purification agent product of producing integrates multiple purification mechanism, has the advantage of organic and inorganic water purification agent concurrently, and is strong to sewage condition adaptability, especially pointed to the mine sewage disposal, embodies characteristics novel, efficient, environmental protection.
Description of drawings
Accompanying drawing is a process flow diagram of the present invention.
Embodiment
Below the specific embodiment of the present invention is elaborated.
Main raw material of the present invention is flyash, hydrochloric acid, oxygenant promotor and organic additive, its proportioning is (pressing solid weight per-cent) 30%～35%, 50%～55%, 10%～15%, 1%～1.5%, 1%～1.5%, and its technical process is: with flyash, hydrochloric acid is raw material, and---------filtration obtains the ferro-aluminum saline solution, and------oxidation, hydrolytic polymerization, copolyreaction---slaking---are isolated liquid water purification agent product or are continued drying and obtain the solid water purifier product to add oxygenant, promotor, organic polymer auxiliary agent in sedimentation in sour molten processing.
Following table is concrete several embodiment of the present invention (weight percent %)
| Flyash | Hydrochloric acid | Oxygenant | Promotor | Organic additive | |
| Embodiment 1 | 35 | 50 | 12 | 1.5 | 1.5 |
| Embodiment 2 | 32.5 | 52.5 | 13 | 1 | 1 |
| Embodiment 3 | 30 | 55 | 12.5 | 1.25 | 1.25 |
Concrete making method of the present invention is, selects various raw materials in proportion, at first accounts for more than 90% to-200 orders flyash is levigate; Add 50～60 ℃ of concentration in proportion and be 37% hydrochloric acid and carry out sour molten reaction, the sour molten reaction times is 2～3 hours, after cooling, filter and make the ferro-aluminum saline solution, again with oxygenant (as H
2O
2) once add in the ferro-aluminum saline solution, oxygenant will once add in the reaction, and reaction effect is better; About 55～65 ℃, carry out the oxydrolysis polyreaction, about 1.5～2 hours; Be warmed up to 80～90 ℃, disposable adding promotor (as ammonium persulphate), adding the concentration that has prepared again is 10% starch or Mierocrystalline cellulose auxiliary agent, the disposable adding of auxiliary agent in the reaction, reaction effect is better, carries out copolyreaction, maintains the temperature at 80～90 ℃, pressure is at 2～2.5 normal atmosphere, and the reaction times was at 4～5 hours; Carry out maturing process then, carry out at normal temperatures, the time is 8～10 hours, obtain liquid composite water purifying agent product,, again liquid product is carried out drying treatment and obtain the solid water purifier product as needs, the purifying water effect of liquid and solid water purifier is the same, its product leading indicator such as following table.
Above-mentioned reaction process uses promotor to be ammonium persulphate, because the selection of promotor is relevant with the selection of oxygenant, when oxygenant selects H
2O
2When (or vitriol oil), promotor is selected ammonium persulphate; When oxygenant selects dense HNO
3The time, promotor is selected cerium ammonium nitrate, and the system that forms promotes the better effects if of copolyreaction like this.
The application invention product with adopt this patent method but do not add auxiliary agent and common polymeric ferric aluminum water purification agent experimentizes, when clarification time and dosing were identical, contrast effect was as follows:
Product when the present invention does not add auxiliary agent as seen from the above table is close with common polymeric ferric aluminum salt performance, and product performance of the present invention obviously are better than the former two, have good purification, settling velocity is fast, temperature influence is little characteristics, stronger to the former water adaptability of high turbidity.Other many tests have also proved same conclusion.
Use product of the present invention, when dosing is identical, can improve decontamination effect improving, reduce settling area, when decontamination effect improving is identical, can significantly reduce dosing, have favorable economic benefit.
Claims (4)
1. the making method of a composite water purifying agent, it is characterized in that, raw material is flyash, hydrochloric acid, oxygenant, promotor and organic polymer auxiliary agent, press solid weight per-cent, be followed successively by 30%～35%, 50%～55%, 10%～15%, 1%～1.5%, 1%～1.5%, its technical process is:
With flyash, hydrochloric acid is raw material, and---------filtration obtains the ferro-aluminum saline solution, and------oxidation, hydrolytic polymerization, copolyreaction---slaking---are isolated liquid water purification agent product or are continued drying and obtain the solid water purifier product to add oxygenant, promotor and organic polymer auxiliary agent in sedimentation in sour molten processing, concrete grammar is, the raw material powder coal ash is levigate to be accounted for more than 90% to-200 orders; Add 50～60 ℃ of concentration in proportion and be 37% hydrochloric acid and carry out sour molten reaction, the sour molten reaction times is 2～3 hours, after the sedimentation to be cooled, filters and makes the ferro-aluminum saline solution; Oxygenant is added in the ferro-aluminum saline solution again, carry out the oxydrolysis polyreaction in the time of 55～65 ℃, the reaction times is 1.5～2 hours; Be warmed up to 80～90 ℃, add promotor, adding the compound concentration that has prepared again is 10% organic polymer auxiliary agent, carries out copolyreaction, maintains the temperature at 80～90 ℃, and pressure is at 2～2.5 normal atmosphere, and the reaction times was at 4～5 hours; Carry out maturing process then, carry out at normal temperatures, the time is 8～10 hours.
2. the making method of a kind of composite water purifying agent according to claim 1 is characterized in that, the organic polymer auxiliary agent of use is: starch or Mierocrystalline cellulose.
3. the making method of a kind of composite water purifying agent according to claim 1 is characterized in that, the oxygenant of use is: H
2O
2Or the vitriol oil or concentrated nitric acid.
4. the making method of a kind of composite water purifying agent according to claim 1 is characterized in that, the promotor of use is: ammonium persulphate or cerium ammonium nitrate, the selection of promotor is relevant with the selection of oxygenant, when oxygenant selects H
2O
2Or during the vitriol oil, promotor is selected ammonium persulphate; When oxygenant selects dense HNO
3The time, promotor is selected cerium ammonium nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101591278A CN101468838B (en) | 2007-12-24 | 2007-12-24 | Method for preparing composite water purification agent |
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|---|---|---|---|
| CN2007101591278A CN101468838B (en) | 2007-12-24 | 2007-12-24 | Method for preparing composite water purification agent |
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|---|---|
| CN101468838A CN101468838A (en) | 2009-07-01 |
| CN101468838B true CN101468838B (en) | 2011-12-07 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103947691B (en) * | 2014-04-18 | 2016-04-27 | 安徽省中日农业环保科技有限公司 | A kind of hydrogen peroxide/polymeric aluminum sulfate silicate compound cyanophyte inorganic agent and preparation method thereof |
| CN104150576B (en) * | 2014-07-20 | 2016-08-31 | 榆林学院 | A kind of coal ash for manufacturing is for the method for PAFC |
| CN105883991A (en) * | 2014-08-29 | 2016-08-24 | 枣庄民兴化工有限公司 | Method for preparing polyaluminium ferric sulfate water purifier by utilization of flyash |
| CN105621568B (en) * | 2015-12-29 | 2019-01-04 | 哈尔滨工业大学 | A kind of preparation method of iron salt solutions |
| CN105905961A (en) * | 2016-06-22 | 2016-08-31 | 江门市江海区炜洁净水材料有限公司 | Composite water purifying agent and preparing method thereof |
| CN110282801A (en) * | 2019-06-26 | 2019-09-27 | 绍兴绿嘉环保科技有限公司 | A kind of technique using Sewage treatment production Polyferric Sulfate water purification agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040101128A (en) * | 2004-11-01 | 2004-12-02 | 서희동 | Purifying agent manufacturing method for treatment of sewage, wastewater, night soil, red tide, green algal ... etc by using peat and fly ash or cinder |
| CN1689979A (en) * | 2004-04-23 | 2005-11-02 | 邵婧鑫 | Making method of ferroaluminosilicate turbid water purifying agent |
| CN1931733A (en) * | 2006-09-06 | 2007-03-21 | 中国科学院生态环境研究中心 | Packaged technology of synthesizing high performance water purifying material with waste plastic and fly ash |
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2007
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1689979A (en) * | 2004-04-23 | 2005-11-02 | 邵婧鑫 | Making method of ferroaluminosilicate turbid water purifying agent |
| KR20040101128A (en) * | 2004-11-01 | 2004-12-02 | 서희동 | Purifying agent manufacturing method for treatment of sewage, wastewater, night soil, red tide, green algal ... etc by using peat and fly ash or cinder |
| CN1931733A (en) * | 2006-09-06 | 2007-03-21 | 中国科学院生态环境研究中心 | Packaged technology of synthesizing high performance water purifying material with waste plastic and fly ash |
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| CN101468838A (en) | 2009-07-01 |
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Address after: 114001 Anshan District, Liaoning, No. 219 Road, No. 39, Tiedong Patentee after: Anshan Iron and Steel Group Mining Co., Ltd. Address before: 114001 Anshan District, Liaoning, No. 219 Road, No. 39, Tiedong Patentee before: Angang Group Mine Company |